Zinc salts of some mercapto compounds as antioxidants of ahigh-temperature ageing of thermoplastic elastomers

(54) Zinc salts of certain mercapto compounds as antioxidants of high-temperature aging of thermoplastic elastomers

Dynamically partially or completely reinforced thermoplastic elastomers containing zinc-defined salts of certain mercapto compounds.

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Zinc salts of some mercapto compounds as antioxidants of high-temperature aging of thermoplastic elastomers

Field of technology

The present invention relates generally to the high temperature aging of dynamically partially or fully crosslinked thermoplastic elastomers. The present invention relates in particular to antioxidants of high-temperature aging of dynamically partially or completely crosslinked thermoplastic elastomers. In particular, the present invention relates to zinc salts of certain mercapto compounds used as antioxidants of high temperature aging of dynamically partially or completely crosslinked thermoplastic elastomers based on polyolefin / ethylene copolymers.

Prior art

Polyolefins and polyolefin composites are typical products that are exposed to elevated temperatures at which their thermo-oxidative degradation is accelerated, called in cases where long periods of use of thermal aging are required or anticipated. Therefore, it is important that polyolefins or polyolefin composites retain their original properties such as elongation at break and tensile strength at elevated temperatures throughout the desired or anticipated period of use. Was found. That antioxidants and their combinations have a retarding and stabilizing effect on the thermal aging of polyolefins and polyolefin composites and therefore their use is widespread. For example, U.S. Patent No. 2,997,456 discloses stabilizing polyolefins against thermal degradation by the addition of metal salts.¹! mercapto compounds of benzimidazole or its selenides or tellurides.

U.S. Patent Nos. 4,226,661 and 4,824,883 disclose the use of antioxidant systems consisting of a combination of a zinc salt of mercaptobenzimidazole with a sterically protected di-tert. butylphenol in polyolefins and similar polymers such as polyethylene or copolymers of ethylene with other monomers.

Japanese Patent 58-122945 discloses a synergistic combination of antioxidants consisting of phenol, 1,2-dihydroshinoline and an organic zinc salt used for olefins to achieve their improved thermal stability.

Although the mentioned additions of antioxidants increase the heat resistance of polyolefin composites, the achieved stability of the original properties is nevertheless low.

Description of the invention

One embodiment of the present invention is directed in part. or a fully dynamically crosslinked thermoplastic elastomer consisting of:

(A) 100 parts of a thermoplastic elastomer containing (i) up to 70 parts of polypropylene polymeric material, (ii) 30 to 70 parts of an amorphous olefin copolymer rubber which is soluble in xylene at normal temperature, (iii) 10 to 30 parts of a semicrystalline copolymer ethylene-propylene or xylene-insoluble ethylene-butene at normal temperature and optionally (iv) 2 to 20 parts of polybutene based on 100 parts (i) (+) (ii) + (iii), and (B) 1.4 to 4.0 parts of zinc mercapto salts of the compound ,, based on 10 CF parts / i / + / ii / + / iii / »while achieving at least 50% preservation of physical properties at elevated temperatures.

Another embodiment of the present invention provides a dynamically fully crosslinked thermoplastic elastomer comprising:

(A) 100 parts of a thermoplastic elastamer containing (i) up to 70 parts of propylene polymeric material and (ii) 80 to 30 parts of amorphous olefin copolymer rubber soluble in xylene at normal temperature, and (B) 1.4 to 4.0 parts of zinc salts of the mercapto compound based on (i) (+) (ii), whereby at least 50% retention of physical properties at elevated temperatures is achieved.

Unless otherwise noted, all parts and percentages are weight # parts and weight # percent

The propylene polymeric material used in the present invention as compound (i) consists of crystalline polypropylene with an isotacticity index higher than 90%, preferably 95-98%, and an ethylene-propylene random copolymer with an ethylene content of up to 10%, preferably from 1% to about 3%, which is from about 90 to about 94% insoluble in xylene at normal temperature. Preferably, the propylene polymer is polypropylene. The propylene polymeric material is present in the partially crosslinked thermoplastic elastomer in an amount of from 30 to 70 parts, preferably from 30 to 50 parts. In the fully crosslinked thermoplastic elastomer, the propylene polymeric material is present in amounts of from 20 to 70 parts, preferably from 50 to 70 parts.

In the partially crosslinked thermoplastic elastomer of the present invention, the amorphous olefin copolymer is soluble in xylene at normal temperature and is present in an amount of from 70 to 30 parts, preferably from 50 to 30 parts. Suitable amorphous olefin copolymer rubbers used in the present invention are rubbers selected from the group consisting of ethylene-propylene copolymer rubber, ethylene-butylene copolymer rubber, ethylene-propylene-unconjugated diene terpene rubber in which the ethylene content is 30 to 70% and the diene content is 1 to 10%, preferably 1 to 5%. The preferred olefin copolymer rubber used is ethylene-propylene copolymer rubber.

The amorphous olefin copolymer contained in the fully crosslinked thermoplastic elastomer is soluble in xylene at normal temperature and is present in amounts of from 80 to 30 parts, preferably from 70 to 50 parts. Examples of the amorphous olefin copolymer used in the fully crosslinked thermoplastic elastomer according to the invention are rubber based on an ethylene-propylene-conjugated diene terpolymer or an ethylene-butene-unconjugated diene terpolymer with an ethylene content of 30 to 70% and a diene content of 1 to 10%. preferably from 1 to 5%. Preferably, the amorphous olefin rubber is an ethylene-propylene-unconjugated diene terpolymer rubber containing 30 to 70% ethylene and 1 to 5% diene.

Examples of * unconjugated dienes include 1,4-hexadiene, ethylidene-norborene and dicyclopentadiene.

The meaning of the term amorphous as used herein is a crystalline phase content of 0 to 22%, preferably 0 to 10% and particularly preferably 0 to 5% measured by differential scanning calorimetry.

The semicrystalline ethylene-propylene or ethylene-butene copolymer (iii) contained in the dynamically partially crosslinked thermoplastic elastomer consists predominantly of ethylene monomer units, i.e. more than 90% of these monomer units, and is insoluble in xylene at normal temperature. The meaning of the term semicrystalline, as used herein, is the content of the crystalline phase from 20 to 60%, preferably from 25 to 50%, measured on the basis of the heat of fusion. ethylene-propyl copolymer or ethylene-butene copolymers, which is determined by differential scanning calorimetry using a 5 to 10 mg sample of this copolymer heated at a rate of 20 ° C / min and provided that the melting point of 100% crystalline polyethylene at 400 ° K is 293 J / .g as described by U. Gaur and B. Wunderlich in? Phys. Chem. Bef. Data, 10/1 /, 119/1981 /. The percentage of crystallinity is calculated by dividing the melting heat of the copolymers by the melting point of 100% crystalline polyethylene and multiplying by 100. Said ethylene-propylene or ethylene-butene copolymer is present in an amount of 8 to 30 parts, preferably 10 to 20 parts. The total amount (1) + (ii) (+) (iii) of the partially dynamically crosslinked composition according to the invention is 100 parts.

If the dynamically partially crosslinked thermoplastic elastomer is polybutene-1 (iv), it is a crystalline isotactic polybutene with a density of from 0.914 to 0.919 g / cm 3, with a melting index of from 1 to 100 g / 10 min. Polybutene-1 is present in the present invention in amounts of from 2 to 20 parts, preferably from 4 to 15 parts, based on 100 parts (i) + (ii) + (iii). The ratio of polybutene-1 to rubber must be less than 0.5, preferably from 0.1 to 0.3.

The zinc salt of the mercapto compound used in the composition of the present invention may be a zinc salt of 2-mercaptobenzothiazole or a zinc salt of 2-mercaptotoluimidazole. The zinc salt is present in an amount of from 1 to 40 parts, preferably from 1.4 to 3 parts, based on 100 parts (A).

The preparation of the dynamically partially crosslinked thermoplastic elastomer according to the invention is carried out using a per oxide vulcanization system comprising an organic per oxide and at least one crosslinker selected from the group of compounds consisting of 1,2-polybutadiene and furo compounds of formula:

- (CH = CH)_E-·^

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wherein X is a group of atoms -CHO, -COOH, -CHONH₂, -CN, -NO₂, -CH₂OOCH₂OOOR, -OH COOR ₂in which R is aryl containing

6-8 carbon atoms or alkyl, containing 1-4 carbon

2 atoms, n is 1 or 2, m is an equal bond number X, R and R are different or identical atoms or groups, which atoms may be hydrogen, alkyls containing 1 to 4 carbon atoms, or cycloalkyl containing 5 to 8 carbon atoms atoms.

The peroxide crosslinker (apparently to be a peroxide sulfurization initiator) must have a half-life of 3.3 to 20 minutes at 160 ° C, preferably

7- 18 min. Suitable examples of peroxides used according to the invention are 1, Abis (tert-butylperoxy-diisopropyl benzene, dicurayl peroxide, n-butyl-4,4'-bis (tert-butylperoxy) valerate and 2,5-di- (tert-butylperoxy) -2,5-dimethylhexane.

The peroxides which are commercially available preparations are used in liquid or solid form in amounts of from 0.5 to 3 parts, preferably from 1 to 2.5 parts, based on 100 parts (i) (+) (ii) (iii).

1,2-Polybutadiene has a molecular weight of from at least 1,300 to 13,000, preferably from 2,400 to 13,000. The content of 1,2-vinyls is at least $ 50, preferably $ 50 to $ 90, and most preferably $ 70 to $ 90. The content of 1,2-polybutadiene is from 2 to 20 parts, preferably from 4 to 12 parts, based on 100 parts (i) (ii) (+) (iii). 1,2-Polybutadiene can be used in liquid or solid form and is commercially available in both forms. When polybutadiene is added in liquid form, it is added in smaller doses of 25-50 $ total. amount for 2 to 6 minutes when added in solid form, the whole amount is dosed at once.

The furan derivatives whose formulas are set forth above and which can be used in the vulcanization systems of the present invention are known in the art and can be prepared according to the method described in U.S. Pat. No. 2,738,338, the method of which is incorporated herein by reference. More suitable examples are

1,5-difurfuryl-1,4-pentadien-3-one, difurfuraldehyde, β- (*.-Furyl) acrolein, 5- (&lt;* .'-furyl) pentadienal, X-furylacrylamide, c-furylacrylonitrile * 6- (x.-furyl) acrylic acid and its esters * esters of furfurylidene and the like Furan derivatives are used in amounts of from 0.15 to 3, preferably in amounts of from 0.17 to 2 parts, based on 100 parts (i). + / ii / + / iii /.

The dynamically partially vulcanized thermoplastic elastomer of the present invention is prepared by adding the peroxide vulcanization system described above to a mixture of components (1), (ii), (iii) and optionally (iv) and bringing the mixture under conditions under which vulcanization takes place while masticating which causes the required dynamic partial vulcanization.

Preferably, the components (i), (ii) and (iii) are prepared in one reactor from a series of reactors, the reaction being carried out in at least two stages by first polymerizing propylene, thereby preparing component (i) and then propylene or butene and ethylene are polymerized in the presence of component (i) and the catalyst used in the first step to prepare components (ii) and (iii). The polymerization can be carried out in the liquid or gas phase or in a mixture of the two phases. Alternatively, the components (i), (ii) and (iii) are prepared separately and then mixed by melt kneading.

The phrase "partially vulcanized" as used herein means that the gel content of cyclohexane as determined by the test described below is a minimum of 80% and a maximum of 94%. Preferably, the gel content is from 85 to 92%.

A phenolic vulcanization system consisting of a halogenated or non-halogenated phenolic resin and a combination of a metal oxide and a halogen donor is used to prepare the fully crosslinked thermoplastic elastomers of the present invention.

The halogenated or non-halogenated vulcanizing resin is present in amounts of from 2 to 10 parts, preferably from 3 to 8 parts * based on 100 parts of amorphous olefin rubber.

Suitable halogenated and non-halogenated vulcanizing primers are accumulated methylol phenolic resins and methylol phenolic resins such as phenolic resins SP-1045

SP-1055 and SP-1056.

The code oxide present in the phenolic vulcanization system is selected from the group consisting of iron oxide, titanium dioxide, magnesium oxide, silica and zinc oxide, preferably the metal oxide is zinc oxide. The metal oxide is present in an amount of from 2 to 10 parts, preferably from 4 to 8 parts * based on 100 parts of amorphous rubber.

Examples of halogen donors used in phenolic vulcanization systems are SnCl₂ . 2H₂0, ZnCl₂ and FeCl 3 · 6H₂0, polychloroprene, chlorosulfonated polyethylene, halogenated butyl rubber and chlorinated paraffin. Halogen donors are present in phenolic vulcanization systems in amounts of from 0.05 parts to 10 parts, preferably from 0.2 parts to 5 parts based on 100 parts of amorphous olefin rubber.

The phrase fully vulcanized as used herein means that the degree of vulcanization determined by the test described below and expressed as a gel content corresponds to a gel content in cyclohexane of at least 97%.

AND

The temperature of mixing and / or mastication is between 15 ° C and 225 ° C, preferably between 170 ° C and 215 ° C, the duration of these operations is from about 2 to 30 minutes *, preferably from 3 to 20 minutes, thus achieving a dynamic partial or complete vulcanization of the thermoplastic elastomer according to the invention. When using partial vulcanization under the above conditions, at least 97% of the peroxide vulcanizing agent decomposes, generally resulting from a theoretical half-life at 160 ° C in ΕΡΌΜ of a decomposition degree of 98-99%. Mastication and kneading can be performed on rollers, in kneaders /e.g. in Banbury or Haake kneaders /, or in single- or twin-spindle extruders.

In the preparation of a partially vulcanized thermoplastic elastomer according to the invention, a mixture of components (i), (ii) and (iii) is preferably prepared in a group of reactors in two stages as described previously, the first stage taking place in liquid propylene and the second stage in the gas phase, use of the catalyst and process described in U.S. Patent Application No. 07 / 551,936 filed April 27, 1990_r which is incorporated herein by reference. If a polybutene component (d) is present in the composition, it is added to a homogeneous mixture prepared as described above and stirred at a temperature sufficient to soften the propylene polymeric material, or at a temperature above the melting point of the polypropylene polymeric material until forms a homogeneous mixture. The crosslinker is added and stirring is continued for about 1 to 2 minutes. Peroxide is then added and stirred until no further change in viscosity occurs for 5 to 7 minutes, indicating that substantially all of the peroxide has been consumed. The massification is continued for a further 1 minute, then the zinc salt of the mercapto compound is added and stirring is continued for a further 1-3 minutes.

The fully crosslinked thermoplastic elastoraer of the present invention is prepared by mechanically mixing the preformed components (i) and (ii). According to this method, the propylene polymeric material, the amorphous copolymer rubber and the zinc salt are mixed at a temperature sufficient to soften the propylene polymeric material or at a temperature above the melting point of the propylene polymeric material until a homogeneous mixture is obtained. A phenolic vulcanization system is then added and the mixture is masticated for 2 to 4 minutes at a temperature high enough to effect vulcanization of the rubber.

In another method, a partially or fully crosslinked thermoplastic elastomer of the present invention may be prepared by first dry blending all components in a drum mixer, e.g., a Henschel mill or a V-blender, which is referred to herein as the premix method. WITH_mG_{s se} it is then charged into the chamber of a high performance kneader, kneaded until a constant viscosity is reached, which requires about 1 to 3 minutes, and then masticated for 1 to 4 minutes.

The peroxidation vulcanization system of the partially crosslinked thermoplastic elastomer may additionally contain other reactive components such as phenylene-bis-maleimide and / or sulfur donors such as alkylphenol disulfides and N, N'-diethylthiourea. The amounts of these other reactive components range from 0.5 to 3 parts, preferably from 1 to 2.5 parts, and the amounts of sulfur donors range from about 0.15 to 3, preferably from 0.17 to 2 parts per 100 parts. parts / i / + / ii / + / iii /.

If the peroxide vulcanization system contains an additional reactive component and / or a sulfur donor, the additional reactive component is generally dosed together with 1,2-polybutadiene and the sulfur donor is usually dosed together with the peroxide.

In addition to the above-mentioned main components, the antioxidant is generally present in the partially or fully crosslinked thermoplastic elastomer in an amount of from 0.1 to 0.9 parts based on 100 parts (A). Examples of antioxidants used in this patent are thiophenols, such as 4,4'-thio-bis- (6-tert-butyl-m-cresol); phosphites such as tris-nonylphenyl phosphite; phenolic esters such as tetrakis (4-methylene (3,5-di-tert-butyl-4-hydroxyhydrocinnamate methane; thiodipropionates such as dilaurylthiopropionate; hydroquinones such as 2,5-di-tert-butylhydrochxone and quinplines such as is 2,2,4-trimethyl-1,2-dihydroquinone.

The partially or fully crosslinked thermoplastic elastamer of the present invention may further contain other conventional additives, e.g., adjusting oils such as paraffinic and naphthenic oils, in an amount of from 20 to 100 parts *, preferably from 25 to 60 parts and most preferably from 25 to 50 parts. based on 100 parts of amorphous alefin copolymer rubber; or zinc oxide in amounts of from 2 to 6 parts, based on 100 parts (A).

If the partially or completely crosslinked thermoplastic elastomer is prepared using a premixing method, the adjusting oil is usually added after the premixed mixture is metered into the kneader and after the melting of the components of the mixture has begun.

10·

The invention will be further illustrated by the following examples. Test specimens were prepared and the properties of these specimens as well as comparative specimens were measured according to the following methods:

<td>tensile strength</td><td>ASTM D - 412</td>

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Gel swelling was determined by swelling a 3.81 cm x 1.90 cm x 0.203 cm sample in about 100 ml of cyclohexah at about 23 ° C, removing the sample and drying it to constant weight (for about 72 hours) in a vacuum oven. at 80 ° C. The percentage gel content was calculated according to the formula:

Original weight The weight of the extracted rubber sample of the rubber sample

Gel content /% / - - x 100

Original weight of the rubber sample

Examples 1-5 of the present invention and Comparative Examples 1-6 serve to illustrate dynamically partially crosslinked thermoplastic elastomers.

Examples of embodiments of the invention

Example 1

By the method described above, a thermoplastic elastomer Hifax RA - 061 was prepared in the reactor, consisting of 40 parts of crystalline polypropylene with an isotactic index of about 22, about 40 parts of ethylene-propylene copolymer with ethylene content of about 50% and 20 parts of semicrystalline substantially linear copolymer. ethylene-propylene insoluble in xylene at normal temperature, containing 96% ethylene. 100 parts of this thermoplastic elastomer were mixed in a Banbury kneader with 4 parts of polybutene, with 20 parts of crystalline polypropylene Pro-fax 6501, which had a melt index of 40 g / min., with 4 parts of 1,2-polybutadiene, with 0.6 parts of alkylphenol sulfide, with 6 parts of ZnO, with 0.3 parts of 4,4'-thio-bis-6-tert.

butyl m-cresol) and 4.2 parts of 1,1'-bis-tert-butylperoxy-2-diisopropylbenzene. The components were mixed at 121 ° C for about 1 to 3 minutes until the polymer melted and the temperature reached 171^p0. Six parts of oil were added and stirring was continued for another 30 to 60 seconds, then the remaining 6 parts of oil were added. Stirring was continued for another 45 to 70 seconds and then 0.6 part of tetrakis [methylene (3,5-di-tert-butyl-4-hydroxyhydrooinnamate)] methane was added. Stirring was continued for another minute until a homogeneous mixture was obtained. The mixture was then filled into the hopper of a single-spindle extruder operating at 200 ° C, and extruded into a water by a circular extruder die, and the obtained string of circular cross-section material was hot-pelleted immediately after leaving the extruder. The obtained pellets were then pneumatically (sucked) transferred to a drying centrifuge and stored.

The pellets thus obtained were loaded into a Haake kneader heated to 182 ° C and kneaded until melting occurred. Then 2.1 parts of zinc salt of 2-mercaptobenzothiazole were added and kneading was continued for about another 2 minutes.

The mixture was then transferred to the bottom plate of a flat mold, covered with the top plate of the mold and pressed at 215 ° C at 10 MPa for 3 minutes. After removal from the hot press, the press plates were transferred to a press operating at normal temperature, cooled at a pressure of 10 MPa for about 15 minutes.^and after removal, the sample was ready for testing.

Physical properties # are listed in Table 1 / Ex. 1 /

Examples 2 and 3

Examples 2 and 3 were prepared using the same procedure and components as in Example 1 except that 1.4 parts and 2.1 parts of 2.1 zinc mercaptobenzimidazole were used instead of 2.1 parts of 2-mercaptobenzothiazole. Physical properties are listed in Table 1 / Ex. 2, Ex. 3 /.

Comparative sample 1

Comparative Sample 1 was prepared according to the procedure and using the components described in Example 1, except that the zinc salt of 2-mercaptobenzothiazole was not used. Physical properties are listed in Table 1 / CT - 1 /.

Comparative samples 2 and 3

Comparative Samples 2 and 3 were prepared according to the procedure and using the components listed in Example 1, except that 1.2 parts were used for Comparative Sample and 1.2 for the Comparative Sample. 3 1.8 parts of the zinc salt of dihutyldithiocarbamate instead of the zinc salt of 2-mercaptobenzothiazole. Physical properties are listed in Table 1 / C - 2; CT - 3 /.

Comparative samples 4 and 5

Comparative Samples 4 and 5 were prepared according to the procedure and using the components set forth in Example 1, except that 1.2 parts were used for Comparative Sample 4 and 1.8 parts of diamine dithiocarbamate zinc salt for Reference Sample 5 instead of zinc salt. 2-mercaptobenzothiazole. Physical properties are listed in Table 1/0 - 3; C - 4 /.

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<td>X</td><td>O</td><td>tí</td><td>X</td><td>KO</td><td>X c</td><td>O</td><td></td><td>t-JX ₍</td><td>O</td><td>í&gt;</td><td>• tí</td><td>• tí</td><td>• tí</td><td>• tí</td>

<td>tí</td><td>X</td><td> 43</td><td> &gt;5</td><td></td><td> &lt;3</td><td>tí</td><td></td><td> » 1 ,</td><td>X</td><td>O</td><td>CQ</td><td>CQ</td><td>CQ</td><td>CQ</td>

<td> 43</td><td>3rd</td><td>X</td><td>ri</td><td>X</td><td>&lt;0 X</td><td> 43</td><td></td><td>X p-</td><td>X</td><td>tí</td><td></td><td></td><td></td><td></td>

<td>tí</td><td rowspan="2"> £</td><td>tí</td><td>O</td><td>what</td><td>XX</td><td>ffi</td><td></td><td>Λ I .fc</td><td>X</td><td>• P</td><td> •</td><td> •</td><td> •</td><td> •</td>

<td>O</td><td>XI</td><td>G.</td><td>ffi</td><td> °</td><td>ri</td><td></td><td>CO X β</td><td>AND</td><td>ffi</td><td>&gt; O</td><td>XJ</td><td>&gt; O</td><td> 30</td>

<td>tí and</td><td>n řs</td><td>X</td><td>1 From</td><td>1 O</td><td>'G. - O</td><td> £</td><td>O</td><td>tí X XX</td><td>PX</td><td>what tí</td><td>43 tí</td><td>43 tí</td><td>43 tí</td><td>43 tí</td>

<td>,O</td><td>tí</td><td>X</td><td> ·*</td><td>tí</td><td>· “Tí</td><td>r- ^</td><td>C</td><td>43 tí &lt;3</td><td>-O</td><td>what</td><td>• P</td><td>• P</td><td>X</td><td>X</td>

<td></td><td>tí.</td><td>ffi</td><td>T-</td><td>ffi</td><td>T- O.</td><td>WHAT</td><td>N</td><td>xx S</td><td>xt co</td><td> 0.</td><td>CD</td><td>CD</td><td>CD</td><td>CD</td>

Η

<td></td><td>WHAT</td><td>he</td><td></td><td></td><td></td><td></td><td></td><td></td><td> 04</td><td></td><td></td><td></td><td></td>

<td></td><td>σκ</td><td>KO</td><td>O</td><td>LT \</td><td> 1</td><td> 1</td><td></td><td>AND</td><td>m</td><td>O</td><td>in</td><td>ir\</td><td>σκ</td>

<td></td><td></td><td>•to</td><td>C-</td><td>st</td><td> 1</td><td> 1</td><td></td><td> 1</td><td>•to</td><td>LfK</td><td> 04</td><td></td><td>he</td>

<td>etc.</td><td>ί O *</td><td></td><td> 4-</td><td></td><td></td><td></td><td></td><td></td><td>b-</td><td></td><td></td><td></td><td></td>

<td>AND</td><td></td><td>T—</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>O</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>O</td><td></td><td></td><td></td><td></td>

<td></td><td> •*4·</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>WHAT</td><td>KO</td><td>O</td><td>τφ</td><td>O</td>

<td></td><td>O</td><td>what</td><td>O</td><td>tr \</td><td> 1</td><td> 1</td><td></td><td></td><td>*to</td><td>•in</td><td> 04</td><td></td><td>'d ·</td>

<td>Μ-</td><td></td><td>*to</td><td>KO</td><td>You·</td><td> 1</td><td> 1</td><td></td><td> 1</td><td>b-</td><td></td><td></td><td></td><td></td>

<td>Ι</td><td>O</td><td>KO</td><td>ir\</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>O</td><td> -</td><td> *—</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td></td><td></td><td></td><td></td><td></td><td></td><td>σκ</td><td></td><td></td><td>he</td><td></td><td></td><td></td><td></td>

<td></td><td>KO</td><td>IfK</td><td></td><td></td><td></td><td>in</td><td></td><td>WHAT</td><td> 00</td><td>rn</td><td>O</td><td>CTx</td><td> 04</td>

<td>he</td><td>KO</td><td>O</td><td>Cr&gt;</td><td></td><td> 1</td><td>•to</td><td></td><td>what</td><td>•to</td><td>KO</td><td> •&gt;4·</td><td></td><td>M</td>

<td> 1</td><td> &gt; -</td><td>"to</td><td>WHAT</td><td></td><td> 1</td><td>what</td><td></td><td></td><td>WHAT</td><td></td><td> 04</td><td></td><td></td>

<td>O</td><td>OK</td><td></td><td>'IN</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td></td><td></td><td> *—</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td></td><td>b-</td><td>CD</td><td></td><td></td><td></td><td></td><td></td><td></td><td>σκ</td><td></td><td></td><td></td><td></td>

<td></td><td>O</td><td>xt</td><td>O</td><td>VO</td><td> 1</td><td></td><td></td><td></td><td>LfK</td><td>KO</td><td>CKJ</td><td>Tť</td><td></td>

<td> 04</td><td></td><td> *»</td><td>LOK</td><td></td><td> |</td><td> |</td><td></td><td> 1</td><td>•to</td><td> *#&gt;</td><td> 04</td><td></td><td></td>

<td> 1</td><td>O</td><td>VO</td><td>ιίκ</td><td></td><td></td><td> 1</td><td></td><td> 1</td><td>b-</td><td></td><td></td><td></td><td></td>

<td>O</td><td> -</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td></td><td>etc.</td><td>VO</td><td></td><td></td><td></td><td> 1</td><td>β</td><td></td><td></td><td></td><td></td><td></td><td></td>

<td></td><td> 04</td><td>what</td><td>O</td><td>cvi</td><td> 1</td><td>O</td><td>&lt;υ</td><td></td><td></td><td></td><td></td><td></td><td></td>

<td> »—</td><td>"to</td><td>•to</td><td>b-</td><td>X} -</td><td> 1</td><td> 4-&gt;</td><td>&gt; N</td><td> 1</td><td> 1</td><td> 1</td><td>AND</td><td> 1</td><td> 1</td>

<td> 1</td><td>σκ</td><td> ”3·</td><td></td><td></td><td></td><td>IN</td><td></td><td> 1</td><td> 1</td><td> 1</td><td> 1</td><td> |</td><td> |</td>

<td>hive</td><td></td><td>T ~</td><td></td><td></td><td></td><td>&gt; O</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td></td><td></td><td></td><td> ·</td><td></td><td></td><td>O.</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td></td><td> 00</td><td>σκ</td><td></td><td></td><td></td><td>KO</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>he</td><td>O</td><td>he</td><td>O</td><td>VO</td><td> 1</td><td>-in</td><td></td><td>• Ό ·</td><td>σκ</td><td>WHAT</td><td> 00</td><td>r-</td><td>KO</td>

<td></td><td>0k</td><td>E*</td><td>'IN</td><td></td><td> 1</td><td>•to</td><td></td><td>σκ</td><td>•to</td><td>b-</td><td></td><td>O</td><td></td>

<td> •</td><td>O</td><td>IfK</td><td></td><td></td><td></td><td>Cfc</td><td></td><td></td><td></td><td></td><td>IN</td><td></td><td></td>

<td></td><td></td><td>T— ·</td><td></td><td></td><td></td><td></td><td></td><td></td><td>r— »</td><td></td><td></td><td></td><td></td>

<td>fxj</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

хυ

04

<img file="CS9201481A3_D0002.tif" />

XI co

E4

<td>m</td><td>m</td><td></td><td></td><td>b-</td><td>b-</td><td></td><td> 04</td><td></td><td></td><td></td>

<td>KO</td><td>KO</td><td>O</td><td>KO</td><td>•to</td><td>σκ</td><td></td><td>he</td><td>b-</td><td>LfK</td><td>m</td>

<td>'* k</td><td>*to</td><td>KĎ</td><td>'IN</td><td>b-</td><td>*to</td><td>O</td><td>•to</td><td>b-</td><td>O</td><td></td>

<td> 00</td><td></td><td>LfK</td><td></td><td> 00</td><td>WHAT</td><td> 1—</td><td>r-</td><td></td><td>• M-</td><td></td>

<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td> 1—</td><td></td><td></td><td></td>

C-

<td></td><td colspan="2"></td><td colspan="2">σκ</td><td colspan="4">b-</td>

<td> *—</td><td>O</td><td>OC— 1</td><td>LfK</td><td></td><td>O</td><td></td><td>IfK</td><td></td>

<td></td><td> ·»</td><td>on η- i</td><td>•to</td><td>The-</td><td>•to</td><td>he</td><td>σκ</td><td></td>

<td>O</td><td>vo</td><td>tn</td><td>σκ</td><td>σ \</td><td>to-</td><td>b-</td><td>he</td><td></td>

<td></td><td>T—</td><td></td><td></td><td></td><td> *—</td><td></td><td></td><td></td>

btJ-

<td colspan="7">XI Ol</td><td colspan="8">Jr. βΙ</td>

<td></td><td>M |</td><td></td><td></td><td></td><td></td><td></td><td>ΌΙ</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td></td><td>βΙ</td><td></td><td></td><td></td><td></td><td></td><td>bH</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td></td><td>ΌΙ</td><td></td><td></td><td></td><td></td><td></td><td>\ l</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td></td><td>Ol</td><td></td><td></td><td>•to</td><td></td><td></td><td>Ol</td><td></td><td></td><td></td><td></td><td>•to</td><td></td><td></td>

<td></td><td>fcl</td><td></td><td></td><td>M</td><td></td><td></td><td>O 1</td><td></td><td></td><td></td><td></td><td>M</td><td></td><td></td>

<td></td><td> &lt;31</td><td></td><td></td><td>β</td><td></td><td></td><td> 1</td><td></td><td></td><td></td><td></td><td>β</td><td></td><td></td>

<td></td><td> 04</td><td></td><td></td><td> «3</td><td></td><td></td><td>IfKl</td><td></td><td></td><td></td><td></td><td> 03</td><td></td><td></td>

<td></td><td> 1</td><td></td><td></td><td>&gt; N</td><td></td><td></td><td>KOI</td><td></td><td></td><td></td><td></td><td>XS3</td><td></td><td></td>

<td></td><td>• rll</td><td></td><td></td><td>here</td><td></td><td></td><td> «—1</td><td></td><td></td><td></td><td></td><td>O</td><td></td><td></td>

<td></td><td>-t-&gt; l</td><td></td><td></td><td> +4</td><td></td><td></td><td> 1</td><td></td><td></td><td></td><td></td><td> 44</td><td></td><td></td>

<td></td><td>rai</td><td></td><td>WHAT</td><td> 03</td><td></td><td></td><td> 31</td><td></td><td></td><td>β</td><td></td><td> 03</td><td></td><td></td>

<td></td><td>Ol</td><td></td><td>Pu</td><td>&gt; o</td><td></td><td></td><td>XI</td><td></td><td></td><td>AND</td><td></td><td>&gt; o</td><td></td><td></td>

<td></td><td>βΙ</td><td></td><td> 2</td><td>O.</td><td></td><td></td><td>Ol</td><td></td><td></td><td> 2</td><td></td><td>AND</td><td></td><td></td>

<td></td><td>-Pl</td><td></td><td></td><td></td><td>AND</td><td></td><td> 31</td><td></td><td></td><td></td><td></td><td></td><td></td><td>AND</td>

<td></td><td>C0I</td><td></td><td>•to</td><td>rl</td><td></td><td></td><td>ΌΙ</td><td></td><td></td><td>•to</td><td></td><td>• H</td><td></td><td></td>

<td></td><td>Ol</td><td> 03</td><td> 0</td><td>&gt; O</td><td> 4)</td><td></td><td>NI</td><td>β</td><td></td><td> 3</td><td></td><td>XO</td><td></td><td> 03</td>

<td></td><td>r4 |</td><td>O,</td><td>X</td><td>AND</td><td> 0</td><td></td><td>fcl</td><td>AND</td><td></td><td>X</td><td></td><td>AND</td><td></td><td>O</td>

<td></td><td>fcl</td><td> 2</td><td>β</td><td></td><td> 0</td><td></td><td></td><td> 2</td><td></td><td>β</td><td></td><td></td><td></td><td>O</td>

<td></td><td> 1</td><td></td><td>+ j</td><td>M</td><td>X</td><td>•to</td><td>βΙ</td><td></td><td></td><td> 44</td><td></td><td>Ή</td><td></td><td>X</td>

<td>fc</td><td>Ό3Ι</td><td>•to</td><td></td><td>β</td><td>ω</td><td> 3</td><td>Cl</td><td>*to</td><td></td><td></td><td></td><td>β</td><td></td><td>ω</td>

<td> +4</td><td> ^41</td><td>O</td><td>fc</td><td> •3</td><td></td><td>AND</td><td> 1</td><td>O</td><td></td><td>fc *</td><td></td><td> 03</td><td></td><td></td>

<td>β</td><td>Hive</td><td>O</td><td></td><td>&gt; Ν</td><td></td><td>OJ</td><td>Jr.</td><td>O</td><td>•to</td><td></td><td></td><td>) N</td><td> •</td><td></td>

<td> 03</td><td>Jr.</td><td>r ~</td><td> 44</td><td> 3</td><td>ÍP</td><td>taú</td><td>4J |</td><td>r- »</td><td> &lt;13</td><td> 44</td><td> &lt;3</td><td> 3</td><td> 03</td><td> 44</td>

<td>β</td><td>βΚ3Ι</td><td></td><td>WHAT</td><td>O</td><td>I</td><td></td><td> 31</td><td></td><td>O</td><td>WHAT</td><td>O</td><td>O</td><td>O</td><td>what</td>

<td>O</td><td>0U4I</td><td>4</td><td>O</td><td>ι — 1</td><td> 0</td><td>X</td><td>β&gt;</td><td> &lt;—1</td><td>β</td><td>O</td><td>β</td><td>rl</td><td>β</td><td>O</td>

<td>β</td><td>Xlfcl</td><td> 3</td><td>β</td><td>Ό</td><td>Ό</td><td>β</td><td> 01</td><td> 3</td><td>Φ</td><td>β</td><td>Φ</td><td>Ό</td><td> 03</td><td>Ό</td>

<td>with</td><td>Ol Ol</td><td>Ό</td><td>fc</td><td>O</td><td>'Í4</td><td>what</td><td>Xíil</td><td>Ό</td><td> 44</td><td>fc</td><td> 44</td><td>O</td><td> 44</td><td>p4</td>

<td>O</td><td>Ol NI</td><td>O</td><td> 4)</td><td>O</td><td></td><td>X!</td><td>4J |</td><td>O</td><td> 03</td><td> 03</td><td> 03</td><td>O</td><td></td><td>fc</td>

<td>fc</td><td>21 fcl</td><td>B</td><td>AND</td><td>O.</td><td> +&gt;</td><td>O</td><td>Wl</td><td>ε</td><td> 0</td><td>AND</td><td> 0</td><td>AND</td><td>iřr</td><td> 44</td>

As can be seen from the data in Table 1, the retention value of the mechanical properties after aging at 165 ° C for 7 days for samples 1 to 3, which contained zinc salts of mercaptans,

50% or more, as compared with the rupture (zero retention) of Comparative Sample 1 and with a retention of less than 50% and with the bloom of Comparative Samples 2 to 5, which contained the commonly used zinc salts of dithiocarbamate compounds.

Examples 4 and 5

The procedure and components are the same as in Example 1, except that 1.4 parts were used for Example 4 and 2 parts of 2-mercaptobenzothiazole zinc salt for the examples, all components except the oil were premixed and Irganox was not added.

/ Ex. 4, Ex. 5 /

Ex. 4 Ex. 5

100 100

4

4

20

4,2 4,2

0,6 0,6

6

0,3 0,3

12

1,4 2,0

The physical properties are listed in the table

Table 2

Hifax RA061 polybutene - 1 1,2-polybutadiene resin Pro-Fay 6501

1,1 * -bis (tert-butylperoxy) diisopropyl 1 benzene alkylphenol disulfide ZnO

4,4 * -thio-bis (β-tert-butyl-m-cresol) paraffin oil zinc salt of 2-mercaptobenzothiazole

Mechanical_Elastics_EŮyodních_yzorních modul 100, MPa tensile strength_r MPa elongation at break /% / Shore D hardness

Air_aging_x_l65_2o / 7day module 100, MPa retention,% tensile strength, MPa

9,48 9,25

15,70 15,94

495 520

41

7,25 7,45

81

8,28 9,66

<td>Table 2 - continued.</td><td>Ex. 4</td><td>Ex</td>

<td>retention,%</td><td> 53</td><td> 61</td>

<td>elongation at break,%</td><td> 360</td><td> 440</td>

<td>retention,%</td><td> 73</td><td> 84</td>

<td>hardness) Shore Ό</td><td> 59</td><td> 59</td>

Example 6

This example is an illustration of a dynamically fully crosslinked thermoplastic elastomer according to the present invention.

40 parts of crystalline polypropylene Pro-fax 6701 with a melt index of 0.8 dg / min, 60 parts of ethylene-propylene-ethylidene-norbornene terpolymer with an ethylidene norbornene content of 4.4% and a Mooney plasticity of 100 / ml 1 + 4 were mixed in a Haake kneader. 121 DEG C. (and 0.1 part of tetrakis [methylene (3,5-ditert-butyl-4-hydroxyhydrocinnamate)] ethane) is likely to be tetrakisethylene (3'5-ditert-butyl-4- hydroxyhydrocinnamate) of methane - note. transl. / at a temperature of 200 ° 0 and 100 rpm. until the polypropylene melted and then for another two minutes. 2 parts of zinc salt of 2-ferrocaptobenzothiazole were added, stirring was continued for another minute and then 3 parts of methylolphenol resin and 0.3 parts of SnGl 2 O 3 H 2 O were added. Stirring was continued for another 3 to 4 minutes until a constant viscosity was reached. Then 4 parts of zinc oxide were added and stirred for about one minute. 5 parts of 10 parts of Sunpar 2280 paraffin oil were added, mixed for 45 to 70 seconds and then? the remaining 5 parts of oil are added.

The mixture was then transferred to the bottom plate of a flat mold, covered with a top plate and pressed at 215 ° C for 3 minutes. at 10 MPa. The press plates were cooled after removal from the press and the sample obtained was used to measure the aging process.

The physical properties are given in Table 3 / Ex. 6 /.

Comparative sample 7

Comparative Sample 7 was prepared according to the procedure and using the components described in Example 6, except that it did not contain the zinc salt of 2-mercaptobenzothiazole. Pysical properties are listed in Table 3 / C - 7 /.

<td>Table 3</td><td>Ex. 6</td><td>C - 7</td>

<td>Pro-fax 6701</td><td> 40</td><td> 40</td>

<td>Epsyn 70 - A</td><td> 60</td><td> 60</td>

<td>tetrakis [methylene (3,5-ditert-butyl-4-hydroxyhydrocinnamate)] methane</td><td> 0,1</td><td> 0,1</td>

<td>phenolic resin SP - tO45</td><td> 3</td><td> 3</td>

<td>ZnO</td><td> 4</td><td> 4</td>

<td>2-mercaptobenzothiazole zinc salt</td><td> 2</td><td> —</td>

<td>paraffin oil Sunpar 2280</td><td> 10</td><td> 10</td>

Mechanical properties of the original samples

<td>module 100, MPa</td><td> 4,87</td><td>A, 78</td>

<td>tensile strength, MPa</td><td> 7,12</td><td> 6,44</td>

<td>elongation at break,%</td><td> 367</td><td> 308</td>

<td>Shore D hardness</td><td> 30</td><td> 25</td>

<td>gel content,%</td><td> 99,3</td><td> 98,8</td>

<td>Air aging, 165 ®C / 7 days</td><td></td><td></td>

<td>module 100, MPa</td><td> 6,21</td><td> «.-,*</td>

<td>retention,%</td><td> 127</td><td> —</td>

<td>tensile strength, Mpa</td><td> 9,66</td><td> 3,28</td>

<td>retention,%</td><td> 135</td><td> 50</td>

<td>elongation at break,%</td><td> 300</td><td> 25</td>

<td>retention,%</td><td> 82</td><td> 8</td>

<td>Shore D hardness</td><td> 29</td><td> 23</td>

Other features, advantages, and embodiments of the invention will be apparent to those skilled in the art from the foregoing description. It follows that, although specific embodiments of the invention have been described in detail, variations and modifications of these specific embodiments fall within the scope of the invention as described and are covered by the following claims.